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A series of La1-xCexCoO3 perovskite nanoparticles with rhombohedral phases was synthesized via sol–gel chemical process. X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), Electron Diffraction Spectroscopy (EDS), Thermogravimetric Analysis (TGA), UV–Vis spectroscopy, Fourier Transform Infrared spectra (FTIR), Nitrogen Adsorption/desorption Isotherm, Temperature Program Reduction/Oxidation (TPR/TPO), X-ray Photoelectron Spectroscopy (XPS) techniques were utilized to examine the phase purity and chemical composition of the materials. An appropriate doping quantity of Ce ion in the LaCoO3 matrix have reduced the bond angle, thus distorting the geometrical structure and creating oxygen vacancies, which thus provides fast electron transportation. The reducibility character and surface adsorbed oxygen vacancies of the perovskites were further improved, as revealed by H2-TPR, O2-TPD and XPS studies. Furthermore, the oxidation of benzyl alcohol was investigated using the prepared perovskites to examine the effect of ceria doping on the catalytic performance of the material. The reaction was carried out with ultra-pure molecular oxygen as oxidant at atmospheric pressure in liquid medium and the kinetics of the reaction was investigated, with a focus on the conversion and selectivity towards benzaldehyde. Under optimum reaction conditions, the 5% Ce doped LaCoO3 catalyst exhibited enhanced catalytic activity (i.e., > 35%) and selectivity of > 99%, as compared to the other prepared catalysts. Remarkably, the activity of catalyst has been found to be stable after four recycles. [ABSTRACT FROM AUTHOR]